Nitrodiphenylamine phosphorus dye compounds



Patented May 13, 1952 NITRODIPHENYLAMINE PHOSPHORUS DYE COMPOUNDS JosephB. Dickey, Rochester, N. Y., assignor to Eastman Kodak Company,Rochester, N. Y., a corporation of New Jersey No Drawing. ApplicationJune 3, 1950,

Serial No. 166,065

7 Claims. (Cl. 260-461) This invention relates to new nitrodiphenylaminephosphorus dye compounds and their ap-.

plication to the art of dyeing or coloring.

The new diphenylamine dye compounds of my invention have the generalformula:

H X QFi group, wherein R1 and R2 each represents an alkyl group having 1to 4, inclusive, carbon atoms, a hydroxyalkyl group having 1 to 4,inclusive, carbon atoms or an alkoxyalkyl group having 3 to l,inclusive, carbon atoms.

Depending upon their particular formula, the new dye compounds of myinvention color a considerable number of materials yellow shades. Thosecompounds which are free of a sulfonic acid group yield yellow dyeingson textile materials made of or containing a cellulose alkyl carboxylicacid ester having two to four carbon atoms in the acid groups thereofwhich have very good iastness to light and gas. These nonsulfonated dyecompounds are especially of importance in' connection with thecoloration of cellulose acetate textile materials. Additionally, theyare useful'as dyes for silk, wool, nylon, fibers from protein orprotein-like materials and plastics and lacquers derived, forexample,from vinyl polymers or cellulose'esters or ethers. The sulfonatedcompounds of my inventionpossess little or no utility for the colorationof cellulose alkyl carboxylic acid ester materials but are useful forthe coloration of the other materials mentioned hereinbefore.

It is an object of my invention to provide new nitrodiphenylaminephosphorus dye compounds. Another object is to provide a satisfactoryprocess for the preparation of the new nitrodiphenylamine phosphorus dyecompounds; "A further object is to provide dyed cellulose alkylcarboxylic acid ester textile materials which possess unusually goodfastne'ss to light=and -gas.- A particular object is toprovidenew-nitrodiphenylamine phosphorus dye compounds which are of especialvalue for the dyeing of celulose acetate textile materials. A stillfurther object is to provide dyed cellulose acetate textile materialswhich possess unusually good fastness to light and gas.

By cellulose alkyl carboxylic acid esters having two to four carbonatoms in the acid groups thereof, I mean to include, for example, bothhydrolyzed and unhydrolyzed cellulose acetate, cellulose propionate,cellulose butyrate, cellulose acetate-propionate and celluloseactate-butyrate.

The new nitrodiphenylamine phosphorus compounds of my invention areprepared by reacting a primary aromatic amine having the formula RNI-Iz,wherein R has the meaning previously assigned to it, with a compoundhaving the formula:

wherein Q represents a chlorine' atom or a bromine atom and X and Y havethe meaning previously assigned to them.

Illustrative -o-alkali formingmetal groups include, for example, the ONagroup, the OK group, the OCa/Z group and the OLi group.

Primary aromatic amines that are used in the preparation of the new,nitrodiphenylamine phosphorus compounds of the invention include, forexample, aniline, o-, mand p-methoxyaniline, o, mand 'p-ethoxya'niline,0-, mand p-n-propoxyaniline, o, mand p-n-butoxyaniline, .o, mandp-toluidine, 0-, mand paminoethylbenzene, o-, mand p-aminopropylbenzene,o-,' mand p-aminobutylbenzene, maminoisopropylbenzene,p-aminophenylethylalcohol, c-aminophenylethylalcohol, p-aminophenyl-B-hydroxyethylether, o-, mand p-chloroaniline, o-, mand p-bromoaniline,o-, mand p-bromoaniline, o-, mand p-fluoroaniline, o-, mandpaminotrifluoro methylbenzene, 0-, mand paminobenzoic acid, 1 amino 21nethoxy-5- methylbenzene, o-, mand p-aminobenzoic acid amide,2,4-dichloroaniline, 2,4-dibromoaniline, o-, 1n andp-aminobenzenesulfonic acid and o-, mand paminobenzenesulfonamide.

For purposes of clarity, it is here noted that the expression amonocyclic aryl nucleus of the benzene series does not and is notintended to include nuclei containing rnore than one benzene ring.

'The following examples illustrate the compounds of my invention andtheir manner of preparation.

Example 1 20 grams of aniline, 20 grams of sodium carbonate and 200 cc.of water are heated together to refluxing conditions and 24 grams of4-chloro 3-nitrophosphonic acid having the formula:

are added portionwise over a period of one hour while refluxing andrefluxing is continued until the evolution of carbon dioxide ceases.Then the unreacted aniline present in the reaction mixture is removed bysteam distillation, following which most of the water present in thereaction mixture is removed by distillation under reduced pressure (e.g. 1-15 mm.). The disodium salt of 4-anilino-3-nitrophenylphosphonicacid crystallizes out as a yellow compound and is recovered bfiltration. It has the formula:

H ONe I O ONa By the use of an equivalent molecular weight of potassiumcarbonate or ammonium carbonate in place of sodium carbonate, thecorresponding potassium and ammonium salt form of the dye is obtained.The free acid form can be obtained by means of treatment with sulfuricacid.

Example 2 By the use of 23 grams of p-toluidine in place of aniline inExample 1, the disodium salt of 4-(4'-methylanilino) 3nitrophenylphosphonic acid is obtained as a yellow compound. It has theformula:

ONa

ONa

The free acid form can be obtained by means of treatment with sulfuricacid.

Example 3 in purified form.

Example 4 30 grams of the N,N-bis-dimethylamide of 4- evolution ofcarbon dioxide ceases.

chloro-3-nitrophenylphosphonic acid having the formula:

CH: N 01- P H) /CH3 l lo: N

and 8.5 grams of sodium bicarbonate are added to cc. of aniline and thereaction mixture resulting is heated at about C. until the Then theunreacted aniline present in the reaction mixture is removed by steamdistillation, following which the reaction mixture is filtered to obtainthe desired dye compound. The precipitate which collects on the filteris crystallized from ethyl alcohol or propyl alcohol to obtain theN,N-bisdimethylamide of 4-anilino-B-nitrophenylphosphonic acid havingthe formula:

C Ha

in purified form.

Example 5 By the use of 100 cc. of p-ethoxyaniline in place of anilinein Example 4, the N,N-bis-dimethylamide of 4 (4'-ethoxyanilino) 3nitrophenylphosphonic acid having the formula:

y N H CHs O O E 0H 3 $07 N/ is obtained.

Example 6 '30 grams of and 8.5 grams of sodium bicarbonate are added to100 cc. of aniline and the reaction mixture resulting is heated at about120 C. until no more carbon dioxide is evolved. Then the unreactedaniline present in the reaction mixture is removed by steamdistillation, following which the reaction mixture is filtered to obtainthe desired dye compound. The precipitate collected on the filter iscrystallized from ethyl alcohol to obtain H /NH2 O-OHzCH CHzOHi NO:

in purified form. v

7 Example 7 By the use of 27 grams of the methyl, ethyl ester of4-chloro-3-nitrophenylphosphonic acid in place of the dimethylester of4-chloro-3-nitrophosphonic acid in Example 3,

OCH;

| O C2115 N02 is obtained as a yellow compound.

Example 8 By the use of 30' grams of the di-n-butylester of4-chloro-3-nitropheny1phosphonic acid in place of the dimethylester of4-chloro-3-nitrophosphonic acid in Example 3,

is obtained as a yellow compound.

Example 9 By the use of an equivalent molecular weight of. the diethy-lester of 4-chloro-3-nitrophenylphosphonic acid in place of the dimethylester of 4-chloro-3-nitrophenylphosphonic acid in Example 3, thecorresponding diethyl ester dye compound is obtained as a yellowcompound.

Example 10 grams of the methyl ester of 4-chloro-3-nitrophenylphosphonamide having the formula:

and 8.5 grams of sodium bicarbonate are reacted with 100 cc. of anilinein accordance with the procedure described in Example 3 to obtain ayellow dye compound.

Example 11 24 grams of 4 chloro 3 nitrophenylphosphondiamide and 8.5grams of sodium bicarbonate are reacted with 100 cc. of anilineinaccordance with the procedure described in Example 3 to obtain:

arereacted with 2e grams or 4-chloro-3-nitrophenylphosphonic acid inaccordance with the procedure described in Example 1. The dye compound n4 ONa A) I ONa I N02 is obtained. The free acid form can be obtained bymeans of treatment with sulfuric acid.

Example 14 38 grams of o-aminobenzenesulfonic acid, 20 grams of sodiumcarbonate and 200 cc. of water are reacted with 27.1 grams of thedimethylester of 4chloro-3-nitrophenylphosphonic acid in accordance withthe procedure described in Exampie 1. The dye compound 0 0 H3 O -G o o oH; s OaNa NO:

is obtained.

Example 15 20 grams of 4-chloro-3-nitropheny1phosphonmono-N-n-butylamideare reacted with 20 grams of aniline in accordance with the proceduredescribed in Example 1. The dye compound obtained has, in its free acidform, the formula:

' H V H N-C4Hn Q K !)\OH N02 Example 16 40 grams of the .N,N-bis-8-hydroxyethylamide of 4-chloro-3-nitrophenylphosphonic acid and 8.5grams of sodium bicarbonate are added to cc. of aniline and the reactionmixture resulting is heated at about C. until the evolution of carbondioxide ceases. Then the unreacted aniline present in the reactionmixture is removed by steam distillation, following which the reactionmixture is filtered to obtain the desired dye compound. The precipitatewhich collects on the filter is crystallized from ethyl alcohol orpropyl alcohol to obtain the N,N-bis-fi-hydroxyethylamide of4-anilino-3-nitrophenylphosphonic acid having the formula:

H H CH OH OH H l 0 N02 N CHzCHzOH in purified form.

Example 17 42 grams of the N,N-bis-e-ethoxyethylamide of4-chloro-3-nitrophenylphosphonic acid and 8.5 grams of sodiumbicarbonate are reacted with 100 cc. of aniline in accordance with theprocedure described in Example 16. The dye compound obtained has theformula:

Example 18 CHzCHzCHzCHzOH Example 19 26 grams of4-chlo-ro-3-nitrophenylphosphonic acid dimethylester are reacted with100 cc. of pn-butoxyaniline in accordance with the procedure describedin Example 3. The dye compound obtained has the formula:

Example 20 30 grams of 4-chloro-3-nitrophenylphosphonic acid di-n-propylester are reacted with 100 cc. of p-amino-n-butylbenzene in accordancewith the procedure described in Example 3. The dye compound obtained hasthe formula:

H omomomcm-O -1 H OCHzCHgCHa N02 Following the precedure describedhereinbefore, the following compounds are readily prepared:

OCHa

OCH:

OCHzCHzCHa Example 21 H oo2H5 1 Jbooma No2 Example 22 OCHa H I O 0011:;No,

Example 23 NHa H 1 C OK i NHz Example 24 H H /N/ Cl- N P GH CHOHCH H i|on N02 Example 25 H H 01120150110113 H oNH, No, N

.5 a Example 26:, g e

A J) OCH: 1 N02 and Example 27 1 H. l a

H CH2 H 7 CH; b l'oz IN In order that the preparation of the compoundsof my invention may be entirely clear, the preparation oi certainintermediates used in their manufacture is described hereinafter.

Example 28 27.4 grams of -chloro-3-nitrophenylphosphonic acid are placedin cc. of phosphorus oxychloride and 25' grams of phosphoruspentachloride are added portionwise. The reaction which takes place iscompleted by Warming on a water bath and then the phosphorus oxychlorideis removed by distilling' under reduced pressure (e. g. l-lO mm). 200cc. of iced Water are then added to-the reaction mixture and thereaction product is taken up with benzene. 4-chloro-3-nitrophenylphosphonic acid dichloride having the formula:

/C1 C1- P Pei NO,

is obtained by crystallization from the benzene. The method abovedescribed is similar to that used by Michaelis, Annalen 181, 314 forpreparing phenylphosphonic acid dichloride t s'I Y) Compounds having theformula:

The materials should be reacted together in the ratio of at least twomolecular equivalent weights of the amine to one molecular equivalentweight of the acid dichloride.

Example 29 10 grams of 4-chloro-3-nitrophenylphosphonic acid dichlorideare dissolved in 100 cc. of acetone 9. and then an excess of ammoniumhydroxide is added at 10 C. The reactionmixture is stirred at 10 C. for4 hours and then pouredintojwater. 4-chloro-3-nitrophenylphosphondiamidehaving the formula:

precipitates as a white crystalline recovered by filtration.

Example 30 10 grams of 4-chloro-3-nitrophenylphosphonic acid dichlorideare dissolved in 50 cc. of ethyl alcohol and heated until no morehydrogen chloride is evolved. The ethyl alcohol is removedbydistillation and then the residue remaining. is distilled under areduced pressure of 'l 2 mm. to obtain the diethylester of4-chloro-3-nitrophenylphosphonic acid. 7

By the use of methyl alcohol, n propyl alcohol, isopropyl alcohol orn-butyl alcohollfor example, in place of ethyl alcohol, thecorrespondingflimethyl, di-n-propyl, diisopropyl or din-butyl ester,respectively, of 4-chloro-3-nitrophenylphosphonic acid is obtained.

Example 31 10 grams of 4-chloro-3-nitrophenylphosphonicacid-dichlorideare dissolved in-l cc. of pyridine and .7 gram of water(1 molecular equivalent of the acid dichloride) is addedand the reactionmixture is warmed to .50 C;'75 C for a few minutes and then cooled. Bythis treatment solid and is is formed.

Example 32 on No,

precipitates and is recovered by filtration.

Example 33 grams of 4-chloro-3-nitropheny1phosphonic acid dichloride aredissolved in 100 cc. of pyridine and 1.18 grams of methyl alcohol (1molecular. equivalent of the acid dichloride) in 10 cc. of

pyridine are added thereto and thereaotion mixture is warmed to 50C.-'75..f.or.1 hour. The methyl ester of4-chloro-3-nitrophenylphosphonic acid monochloridehavingthe formula:

- OCH:

is formed. (This compound can-be precipitated from the reaction mixtureby pouring the reaction mixture into ice-co1d. water,. ater which thecompound is recovered. by, filtration.)-

was

1. Example 34 .7 gram of water (1 molecular equivalent; of thephenylphosphonic acid compound) is added to the reaction mixtureobtained as described inExample 33 and the reaction mixture is heated to50 vC.-,-" C. for 1 hour. The methyl ester of4'-chlor0-3nitrophenylphosphonic acid having the'formula:

Ga Y t N a cm is formed. It is precipitated from the reaction mixture bypouring the reaction mixture into ice-cold water, after which it isrecovered by filtration, washed with cold water and dried.

Example 36' 10 grams of 4-chloro-3-nitrophenylphosphonic acid dichlorideare dissolved in cc. of acetone and 10 grams of ethanolamine are added.The reaction mixture is warmed to 50 C.'75 0., stirred at thistemperature for 1 hour and then poured. into ice-cold water. TheN,N-bis-;3- hydroxyethylamide of l-chloro 3 nitrophenylphosphonic acidhaving the formula:

N v CH2CH2OH N oz N omomon precipitates and is recovered by filtration.

Example 37 By the use of 14 grams of B-ethoxyethylamine in place ofethanolamine in Example 36, the N ,N bis -plethoxyethylamide of 4 chloro-3- nitrophenylphosphonic acid is obtained.

Example 38' By the use of 8 grams of dimethylamine in place ofethanolamine in Example 35, the N,N bis-dimethylamide of 4 chloro 3nitrophenylphosphonic acid having the formula:

CHs -0-1 l lo} $\N/ CHa is obtained.

Example 39 grams of 4-chloro-3-nitrophenylphosphonic acid dichloride aredissolved in 50 cc. of methyl alcohol and the reaction mixture is heateduntil no more hydrogen chloride is evolved. The methyl alcohol isremoved by distillation and then the residue remaining is distilledunder a reduced pressure of 1-2 mm. to obtain the dimethyl ester of 4chloro 3 nitrophenylphosphonic acid.

Example 40 10 grams of 4-chloro-3-nitrophenylphosphonic acid dichlorideare dissolved in 50 cc. of n-butyl alcohol and the reaction mixture isheated until no more hydrogen chloride is evolved. The nbutyl alcohol isremoved by distillation and then the residue remaining is distilledunder a reduced pressure of 1-2 mm. to obtain the di-nbutyl ester of4-chloro-3-nitrophenylphosphonic acid.

Example 41 10 grams of 4-chloro-3-nitrophenylphosphonic acid dichlorideare dissolved in 50 cc. of n-propyl alcohol and the reaction mixture isheated until no more hydrogen chloride is evolved. The n-propyl alcoholis removed by distillation and then the residue remaining is distilledunder a reduced pressure of 1-2 mm. to obtain the di-npropyl ester of4-chloro-3-nitrophenylphosphonic acid.

Example 42 10 grams of 4-chloro-3-nitrophenylphosphonic acid dichlorideare dissolved in 100 cc. of pyridine and 2.74 grams of n-butyl alcohol(1 molecular equivalent of the acid dichloride) in 10 cc. of pyridineare added thereto and the reaction mixture is warmed to 50 C.'l5 C. for1 hour. The n-butyl ester of 4-chloro-3-nitrophenylphosphonic acidmonochloride is formed. (This compound can be precipitated from thereaction mixture by pouring the reaction mixture into icecold waterafter which the com-pound is recovered by filtration.)

Example 43 The reaction mixture obtained as described in Example 42 and3 grams of ammonia are heated together with shaking in an autoclave at50 C.- 75 C. for 1 hour. The n-butyl ester of l-chloro-3-nitrophenylphosphonmonoamide having the formula:

is formed. It is precipitated from the reaction mixture by pouring thereaction mixture into ice-cold water after which it is recovered byfiltration, washed With cold water, and dried.

Example 44 The reaction mixture obtained as described in Example 33 isheated to 50 C.'75 C. for 1 hour with 3 grams of ethyl alcohol. Themethyl, ethyl ester of 4-chloro-3-nitrophenylphosphonic acid is formed.It is precipitated from the reaction mixture by pouring the reactionmixture into ice-cold water after which it is recovered by filtration,washed with cold water, and dried.

Example 45 The reaction mixture obtained as described in Example 33 isheated in an autoclave with 3' V 12 grams of ammonia at 50 C.-75 C. for1-2 hours. The methyl ester of 4-chloro-3-nitrophenylphosphonamide isformed. It is precipitated from the reaction mixture by pouring thereaction mixture into ice-cold water after which it is recovered byfiltration, washed with cold water, and dried.

Example 46 10 grams of n-butylamine are added to the reaction mixtureformed in Example 31 and the reaction mixture is warmed to 50 C. andmaintained at this temperature for about 30 minutes after which it ispoured into water. 4-chloro-3- nitrophenylphosphonmono-N-n-butylamideprecipitates and is recovered by filtration.

Example 47 10 grams of 4-chloro-3-nitrophenylphosphonic acid dichlorideare dissolved in 100 cc. of acetone and 20 grams of2,3-dihydroxypropylamine are added. The reaction mixture is warmed to 50C.-'75 C., stirred at this temperature for 1 hour and then poured intoice-cold water. The N,N-bis43, -dihydroxypropylamide of 4-ch1oro-3-nitrophenylphosphonic acid precipitates and is recovered byfiltration,

Example 49 10 grams of 2,3-dihydroxypropylamine are added to thereaction mixture formed in Exampic 31. The reaction mixture is warmed to50 C. and maintained at this temperature for about 30 minutes afterwhich it is poured into Water. 4-chloro-B-nitrophenylphosphonic acidN-2,3-dihydroxypropylamide having the formula:

precipitates and is recovered by filtration.

The nitrodiphenylamine phosphorus dye compounds of my invention can beapplied to the textile materials named hereinbefore in the form of anaqueous dispersion and are ordinarily so applied. To illustrate, the dyecompound is finely ground with a dispersing agent such as sodium lignumsulfonate, Turkey red oil, soap, or an oleyl glyceryl sulfate and theresulting mixture is dispersed in water. The dye bath thus prepared isheated to a temperature approximating 45 C.- 55 C. and the textilematerial to be dyed is immersed in the dye bath, following which thetemperature is gradually raised to C.- C. and maintained at thistemperature until dyeing is complete, usually one-half to two hours.From time to time throughout the dyeing operation, the material isworked to promote even dyeing. Upon completion of the dyeing operation,the textile material is removed from the dye bath, washed with anaqueous soap solution, rinsed well with Water and dried.

The procedure just described is applicable whether the dye compoundcontains a sulfonic acid group or not. The dye compounds of theinvention not containing a sulfonic acid group are, for the most part,practically water-insoluble. Where a sulfonic acid group is present, theWater solubility is increased and in such case a greater amount of thedye will go into solution.

Widely varying amounts of dye can be used in the dyeing operation. Theamount of dye used can be, for example, 54; to 3% (by weight) of that ofthe textile material although lesser or greater amounts of dye can beemployed.

I claim:

1. The diphenylamine compounds having the general formula:

X RN P wherein R represents a monocyclic aryl nucleus of the benzeneseries and X and Y each represents a member selected from the groupconsisting of a hydroxyl group, an -o-alkali forming metal group, an--ONH4 group, an alkoxy group having 1 to 4, inclusive, carbon atoms, anamino group and an N Rz group, wherein R1 and R2 each represents amember selected from the group consisting of an alkyl group having 1 to4, inclusive, carbon atoms, a hydroxylalkyl group having 1 to 4,inclusive, carbon atoms and an alkoxyalkyl group having 31:0 4,inclusive, carbon atoms.

2. The diphenylamine compounds having the general formula:

wherein R. represents a monocyclic aryl nucleus of the benzene seriesand the alkali and ammonium salts thereof.

3. The diphenylamine compounds having the general formula:

wherein X represents an alkoxy group having 1 14 to 4, inclusive, carbonatoms and the alkali and ammonium salts thereof.

4. The diphenylamine compounds having the general formula:

wherein X represents an alkyl group having 1 to 4, inclusive, carbonatoms and the alkali and ammonium salts thereof.

5. The diphenylamine compound having the formula:

OCH: H O Q (k O CH: NO:

6. The diphenylamine compound having the formula:

7. The diphenylamine compound having the formula:

JOSEPH B. DICKEY.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,618,415 Ellis Feb. 22, 19271,947,038 Ellis Feb. 13, 1934 2,200,343 Ritter May 14, 1940 2,474,333Seymour June 28, 1949

1. THE DIPHENYLAMINE COMPOUNDS HAVING THE GENERAL FORMULA: 